Light-Activated Pesticides - ACS Publications - American Chemical

Chapter 5

Singlet Oxygen Quantum Yields Michael A. J. Rodgers Downloaded by MICHIGAN STATE UNIV on October 26, 2014 | http://pubs.acs.org Publication Date: May 7, 1987 | doi: 10.1021/bk-1987-0339.ch005

Center for Fast Kinetics Research, University of Texas at Austin, Austin, TX 78712

The lowest excited state of molecular oxygen (also known as dioxy gen) has the spectroscopic notation O ( Δ ). Its v=0 vibrational level lies 7880 cm (1eV; 23kcal/mol) above the v=0 level of the molecular ground state (3Σ-g) The Δ —> 3Σ-g transition and its inverse are strongly forbidden for electric dipole radiation in the isolated molecules -- at zero pressure in the gas phase the radiat ive lifetime of O ( Δ ) is calculated to be 45 mins.(1). This property is apparently phase dependent since a value of 4s has been reported in carbon tetrachloride (2). This forbiddeness of the op tical transition makes generation of O ( Δ ) by direct-photon ab sorption very difficult to accomplish although quantities sufficient to allow kinetic studies in Freons have been produced by irradiation of high pressures of O in Freon solution with 1.064 μm radiation from a high power Nd: YAG laser (3). The extremely low probability of the radiative transition has several consequences, the one that is pertinent to this account concerns the use of indirect methods of producing O ( Δ ) for quan titative kinetic studies. Such investigations are generally per formed in one of two ways. (i) Singlet oxygen is formed at a constant rate by applica tion of some perturbation that operates continuously. The progress of reactions are followed by measuring the yields of chemical prod ucts or other effects as a function of time over which the pertur bation is continued. (ii) Singlet oxygen is formed by a short high, intensity burst of the perturbing effect such that the concentration of singlet oxygen produced is sufficient to be followed, either directly or indirectly, in timer-resolved experiments. Both kinds of experiment are capable of yielding kinetic data of interest such as natural lifetimes, reaction rate constants, quenching rate constants and so forth. The perturbation effect most often employed is that of photo excitation of a sensitizer. This act forms upper singlet sensi tizer states that can undergo inter-system crossing to triplet states (Reactions 1-4). 1

2

g

-1

1

g

1

2

g

1

2

g

2

1

2

g

0097-6156/87/0339-0076$06.50/0 © 1987 American Chemical Society

In Light-Activated Pesticides; Heitz, J., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1987.

5.

RODGERS

Singlet Oxygen Quantum Yields S + hv 1 *

> „

S

1

S* 1 * S

Subsequently, (5) and (6)

(1)

1s*

>

s

> >

s

+

h

V

( )

F

2

3s*

(3) (4)

the t r i p l e t s t a t e can decay a c c o r d i n g t o R e a c t i o n s

3s* 3 *

> o

~

S

Downloaded by MICHIGAN STATE UNIV on October 26, 2014 | http://pubs.acs.org Publication Date: May 7, 1987 | doi: 10.1021/bk-1987-0339.ch005

77

S + hv s

(5) (6)

p

In the above scheme hvp and hvp r e f e r t o the r a d i a t i v e p r o c e s s e s denoted as f l u o r e s c e n c e ( R e a c t i o n 2) and phosphorescence ( R e a c t i o n 5) r e s p e c t i v e l y . For most s e n s i t i z e r s i n f l u i d media t h e phosphorr e s c e n t channel c o n t r i b u t e s o n l y m i n i m a l l y t o the t o t a l decay o f the t r i p l e t s t a t e p o p u l a t i o n . ( 4 ) When oxygen i s d i s s o l v e d i n t h e s o l v e n t ( a e r a t e d s o l v e n t s a r e n o r m a l l y employed) the f o l l o w i n g a d d i t i o n a l r e a c t i o n s a r e p o s s i b l e . is*

+

0 (3z )

-

1s*

• 0 (3zg)

-

1s*

+

°2( ^i)

~

3s*

• 0 (3z-g)

-

3S*

+

-

2

g

2

3

2

0 (3z-g) 2

> > > > >

3s*

+ 0 (lA ) 2

(7)

g

(8)

1

s + 0 ( A ) 2

g

s + 0 (3z )

(9)

s + 0 (3z )

(10)

s + 0 (lA )

(11)

2

2

2

g

g

g

C l e a r l y R e a c t i o n (7) i s s p i n - a l l o w e d but i s o n l y p o s s i b l e when (E -ET^EA). R e a c t i o n (8) i s s p i n f o r b i d d e n and R e a c t i o n (9) has s e v e r e Franck.-Condon r e s t r i c t i o n s i n t h a t the energy o f 1s* has t o be d i s s i p a t e d i n t o v i b r a t i o n a l modes. S i m i l a r r e s t r i c t i o n s a p p l y to R e a c t i o n (10) which i s i n c o m p e t i t i o n w i t h R e a c t i o n (11), t h e s i n g l e t oxygens-producing channel from s e n s i t i z e r t r i p l e t s t a t e s . S

RATIONALE FOR MEASURING SINGLET OXYGEN QUANTUM YIELDS The r e a s o n why t h e r e s h o u l d be s o much i n t e r e s t i n d e t e r m i n i n g quantum y i e l d s o f s i n g l e t oxygen f a l l i n t o two major c a t e g o r i e s , one c o n c e r n i n g fundamental p h o t o p h y s i c s , the o t h e r c o n c e r n i n g apr plications of photosensitized oxidation. The p h o t o p h y s i c s requirement concerns expanding our knowledge about the i n t e r a c t i o n s o f the s e n s i t i z e r e x c i t e d s t a t e s w i t h oxygen as summarized i n R e a c t i o n s (7) through (11) above. Q u a n t i t a t i v e measurement o f the y i e l d s of 0 2 ( A ) produced from m o l e c u l a r singr. l e t s t a t e s and m o l e c u l a r t r i p l e t s t a t e s a i d s i n a s s e s s i n g the amount t h a t a p a r t i c u l a r r e a c t i o n c c h a n n e l c o n t r i b u t e s t o the over* a l l d e a c t i v a t i o n . I n f o r m a t i o n on how the y i e l d s v a r y w i t h i n f l u r ences such as s e n s i t i z e r s t r u c t u r e , s t a t e energy, n a t u r e o f s o l v e n t and s o on i s i m p o r t a n t i n p r o v i d i n g m e c h a n i s t i c i n f o r m a t i o n . The quenching o f e x c i t e d s t a t e s by oxygen i s such a w e l l know p r o c e s s t h a t i t may be s u r p r i s i n g t o many t o l e a r n t h a t i t i s s o l i t t l e understood. 1

g



78

LIGHT-ACTIVATED PESTICIDES

The a r e a o f p h o t o s e n s i t i z e d o x i d a t i o n s i s v e r y wide, r a n g i n g over a l l systems where the combined a c t i o n of v i s i b l e l i g h t , an a b s o r b i n g m o l e c u l e or r e s i d u e , and m o l e c u l a r oxygen can r e s u l t i n p h o t o c h e m i c a l damages ( 5 ) . T h i s c o m b i n a t i o n has impact i n such d i v e r s e p l a c e s as the t e x t i l e i n d u s t r y , the cancer c l i n i c and the p l a n t l e a f . T e x t i l e t e c h n o l o g i s t s a r e concerned w i t h the photof a d i n g and p h o t o d e s t r u c t i o n o f f i b e r s t h a t have been dyed w i t h v i s i b l e l i g h t a b s o r b i n g pigments; i n the cancer c l i n i c t r i a l s a r e p r o c e e d i n g i n which p o r p h y r i n doped tumors undergo n e c r o s i s when i r r a d i a t e d with red l i g h t ; the p h o t o s y n t h e t i c a p p a r a t u s o f green p l a n t s a r e i d e a l l y s u i t e d f o r p r o d u c i n g s i n g l e t oxygen from photoe x c i t e d c h l o r o p h y l l m o l e c u l e s -.- the presence o f c a r o t e n o i d s o f f e r s non-damaging p h y s i c a l modes o f d e a c t i v a t i n g c h l o r o p h y l l t r i p l e t s t a t e s . P r o c e s s e s such as t h e s e , t o g e t h e r w i t h the a c t i o n o f l i g h t - a c t i v a t e d p e s t i c i d e s , f a l l under the g e n e r a l heading of photodynamic a c t i o n , i e damage i n c u r r e d i n a b i o l o g i c a l system through the p h o t o s e n s i t i z e d o x i d a t i o n mechanisms (6). There i s a w e a l t h o f e v i d e n c e i n d i c a t i n g the involvement o f s i n g l e t oxygen as a p r i m a r y r e a c t i v e s p e c i e s i n one c l a s s o f photodynamic a c t i o n . Thus the more q u a n t i t a t i v e i n f o r m a t i o n t h a t we can o b t a i n about the y i e l d s of s i n g l e t oxygen i n photodynamic c i r c u m s t a n c e s , then the g r e a t e r our o p p o r t u n i t y f o r u n d e r s t a n d i n g the d e t a i l e d mechanism and a l t e r r i n g , (enhancing or d i m i n i s h i n g , a c c o r d i n g t o the r e q u i r e m e n t s ) i t s effects. SINGLET STATE SOURCES A c o n s i d e r a t i o n o f R e a c t i o n s ( 7 ) , (10) and (11) shows t h a t f o r s e n s i t i z e r s h a v i n g a s u f f i c i e n t S-T energy d i f f e r e n c e , each ^S* s t a t e (_ie each photon) w i l l g i v e r i s e , i n the l i m i t , t o two 0 2 ( ^ A ) m o l e c u l e s — R e a c t i o n (7) f o l l o w e d by R e a c t i o n ( 1 1 ) , _ie t h e s i n g l e t oxygen quantum y i e l d (*^) can approach 2.0. Several researchers (7-9) have i n v e s t i g a t e d such p r o c e s s e s and e v i d e n c e f o r *^ v a l u e s g r e a t e r than u n i t y has been o b t a i n e d . S u b s t i t u t e d anthracenes and h i g h e r homologues show t h i s e f f e c t . Of c o u r s e , the l i m i t i n g quanc-turn y i e l d i s r a r e l y a c h i e v e d s i m p l y because a t oxygen c o n c e n t r a tions attainable i n 0 -saturated organic solvents ( t y p i c a l l y l O ^ M ) , the product ky[02] i s u s u a l l y unable t o outweigh the sum ( k + k3 + kij) i e , s i n g l e t s t a t e s a r e g e n e r a l l y l o s t t o the unimol e c u l a r decay modes w i t h a p p r o x i m a t e l y s i m i l a r e f f i c i e n c y t o t h a t w i t h which they a r e quenched by oxygen. g

2

2

TRIPLET STATE SOURCES With m o l e c u l e s t h a t have Es - Ej< E^, R e a c t i o n (7) i s not energetic a l l y f e a s i b l e and s i n c e R e a c t i o n (8) i s s p i n - f o r b i d d e n , the o n l y source o f 0 ( A ) from e x c i t e d s t a t e s o f many systems i s through the t r i p l e t m a n i f o l d s v i a oxygen quenching. I n many m o l e c u l a r systems, oxygen quenching o f t r i p l e t s t a t e s i s the o n l y p r o c e s s f o r s i n g l e t oxygen p r o d u c t i o n . R e a c t i o n (11) above can be expanded i n t o the s e t ( R e a c t i o n s 11a-c) as below and i n q u a n t i t a t i v e terms, c o m p e t i t i o n between the s e t determines the r a t e s o f 0 ( A ) f o r m a t i o n and t h e quantum yields. 1

2

g

1

2

g


5.

RODGERS

Singlet Oxygen Quantum Yields

3s* + 02(3zg) ^==i

79

1(S—0 )»

->

S + 0 ( A )

(11a)

3(S—0 )*

->

S + 0 (3Eg)

(11b)

2

2

1

2

G

2

5(S~0 )*

(11c)

2

The s p e c i e s 1 i 3 , 5 ( s — 0 ) * r e p r e s e n t s the t r a n s i t i o n s t a t e between r e a c t a n t s and p r o d u c t s . The mutual t r i p l e t m u l t i p l i c i t y of the r e a c t a n t s conveys n i n e p o s s i b l e degenerate s p i n s u b ^ s t a t e s w i t h i n the t r a n s i t i o n s t a t e ; the s i n g l e t and t r i p l e t e n t i t i e s have e n e r g e t i c a l l y r e a c h a b l e product s t a t e s but the q u i n t e t s have not and they must r e t u r n t o r e a c t a n t s t a t e s . The consequence o f t h i s i s t h a t the r a t e c o n s t a n t f o r s i n g l e t oxygen f o r m a t i o n w i l l not be l a r g e r than one n i n t h of the v a l u e of the r a t e c o n s t a n t f o r d i f f u s i o n - l i m i t e d quenching i n the medium (J_0). That the measured r a t e c o n s t a n t s f o r oxygen quenching o f the t r i p l e t s t a t e s o f many m o l e c u l e s f a l l c l o s e t o t h i s one n i n t h of d i f f u s i o n c o n t r o l v a l u e (near 2 x 109 1 m o l ~ s " ) has been t a k e n as an i n d i c a t i o n (1_0) t h a t i n s u c h i n s t a n c e s the s i n g l e t c h a n n e l ( R e a c t i o n 11a) p r o v i d e s the o n l y t r i p l e t d e a c t i v a t i o n mechanism, t h e r e b y l e a d i n g t o 0 ( A ) quantum y i e l d s o f u n i t y . However, more d e t a i l e d o b s e r v a t i o n s show (11-13) t h i s i s not n e c e s s a r i l y t r u e and t h a t the system i s more c o m p l i c a t e d than f i r s t thought. The y i e l d o f 0 ( l A ) formed from a m o l e c u l a r t r i p l e t s t a t e i n v o l v e s a c o m p e t i t i o n between R e a c t i o n s (10) and (11) and the parameter S was c o i n e d (1J_) t o d e s c r i b e t h i s where


2

1

r

1

1

2

2

g

g

A

SA = k i / ( k 1

1 1

+

k ) 1 0

or, S i s the f r a c t i o n o f t r i p l e t quenchings by oxygen t h a t l e a d s t o s i n g l e t oxygen. Thus i n a p h o t o c h e m i c a l system t h a t i n v o l v e s 0 ( ^ A g ) f o r m a t i o n v i a s e n s i t i z e r t r i p l e t s t a t e s o n l y , we see t h a t A

2

S

*A = A'*T where

M0

g

2

> product


(13)

80


Perhaps t h e most w i d e l y - u s e d s u b s t r a t e (M) has been d i p h e n y l i s o b e n z o f u r a n (DPBF) which, on r e a c t i o n w i t h s i n g l e t oxygen l o s e s i t s c h a r a c t e r i s t i c y e l l o w c o l o r . I n i t i a l l y DPBF was employed (14-17) i n s i t u a t i o n s where k i n e t i c d a t a were b e i n g e v a l u a t e d . L a t e r t h e e x t e n t o f b l e a c h i n g became employed i n y i e l d e v a l u a t i o n s (11,18-20). Singh e t a l (21_) have o u t l i n e d t h e p o t e n t i a l d i f f i c u l t t i e s i n u s i n g DPBF as a q u a n t i t a t i v e probe f o r s i n g l e t oxygen i n c o n t i n u o u s i l l u m i n a t i o n c o n d i t i o n s . I n t i m e r - r e s o l v e d experiments these problems a r e l e s s s e v e r e but c a u t i o n i s always n e c e s s a r y on account o f the m o l e c u l e ' s h i g h p h o t o s e n s i t i v i t y . L i k e DBPF, some condensed p o l y c y c l i c a r o m a t i c hydrocarbons ( r u b r e n e , 9,10 d i p h e n y l anthracene) form endoperoxides w i t h 0 2 ( A ) - a r e a c t i o n t h a t r e moves extended chromophores and l e a d s t o b l e a c h i n g . These m o l e c u l e s have a l s o been used f o r q u a n t i t a t i v e y i e l d e v a l u a t i o n s (7-9,22,23) In d e t e r m i n i n g t h e y i e l d o f s i n g l e t oxygen from a s e r i e s o f r o s e bengal d e r i v a t i v e s , Neckers e t a l have employed 2,3 d i p h e n y l - d i o x e n e as a probe f o r 0 ( A ) . T h i s s p e c i e s i s o x i d i z e d t o an a c y c l i c e s t e r which was q u a n t i f i e d gas c h r o m a t o g r a p h i c a l l y (24,25). Another method has been t o use p a r a - n i t r o s o d i m e t h y l a n i l i n e (RNO) a g r e e n - c o l o r e d m o l e c u l e - as a r e a c t i v e probe f o r t r a n s a n n u l a r p e r o x i d e s (M0 ) formed from s i n g l e t oxygen r e a c t i o n w i t h i m i d a z o l e s . A g a i n t h e c o l o r a t i o n o f M i s l o s t and t h i s p r o p e r t y i s f o l lowed q u a n t i t a t i v e l y t o r e s u l t i n * v a l u e s (23,26). Those c h e m i c a l probe systems t h a t depend on a s i m p l e c o l o r change can be, and have been employed i n both s t e a d y - s t a t e and t i m e - r e s o l v e d e x p e r i m e n t a l t i o n . Of c o u r s e i n u s i n g r e a c t i v e monitor m o l e c u l e s (DPBF, rub«r e n e , e t c . ) f o r quantum y i e l d measurement i t i s i m p o r t a n t t o know what f r a c t i o n o f t h e d e a c t i v a t i n g encounters l e a d s t o s u b s t r a t e l o s s . For DPBF t h i s f r a c t i o n i s a p p a r e n t l y u n i t y (27). I n r e c e n t y e a r s r e s e a r c h e r s have been u s i n g such i n d i r e c t c h e m i c a l probe t e c h n i q u e s l e s s , and newly-developed d i r e c t spectror. s c o p i c methods more. The use o f c h e m i c a l probes can be s u b j e c t t o problems a r i s i n g o u t o f u n c e r t a i n t i e s i n r e a c t i o n mechanisms w i t h d i f f e r e n t s e n s i t i z e r s . A l s o they r e q u i r e extreme c a r e i n e x c l u s i o n o f extraneous l i g h t . The advent o f f a s t response d e t e c t o r s w i t h i n f r a r e d s e n s i t i v i t y and h i g h bandwidth, h i g h g a i n a m p l i f i e r s has g i v e n t h e c a p a b i l i t y o f d e t e c t i n g t h e very weak luminescence a t 1.269 urn ( F i g u r e 1) r e s u l t i n g from the 3z~ < l A transition i n oxygen. The f o r b i d d e n e s s o f t h i s t r a n s i t i o n r e s u l t s i n l u m i n e s r cence quantum y i e l d s b e i n g v e r y low. The e a r l i e s t work i n t h i s a r e a was c a r r i e d o u t by R u s s i a n workers who p i o n e e r e d luminescence d e t e c t i o n i n both c.w. (28) and time«-.resolved modes ( 2 9 , 3 0 ) . These e a r l y e f f o r t s were r a p i d l y f o l l o w e d by a c t i v i t y i n t h e U.S. where r e d - s e n s i t i v e p h o t o m u l t i p l i e r d e t e c t o r s were r e p l a c e d by i n f r a r e d d e t e c t i n g photodiodes backed-up by h i g h g a i n a m p l i f i e r s f o r cont i n u o u s wave (c.w.) ( 3 D and t i m e - r e s o l v e d work (32-35). This t e c h n o l o g y has r e v o l u t i o n i z e d 0 2 ( A ) d e t e c t i o n because o f i t s d i r e c t n e s s , p r e c i s i o n , convenience and r a p i d i t y . The v a s t m a j o r i t y o f r e s e a r c h on 0 ( A ) u s i n g i n f r a r e d luminescence t e c h n i q u e s has concerned k i n e t i c s t u d i e s but t h e s e methods a r e a l s o a p p l i c a b l e t o quantum y i e l d s t u d i e s once t h e proper c a l i b r a t i o n has been c a r r i e d o u t . T h i s c a l i b r a t i o n p r o c e s s i s e s s e n t i a l and i t i s d e s c r i b e d i n some d e t a i l below. 1


g

1

2

g

2

A

g

1

g

1

2

g



RODGERS

1200


nm

1300

F i g u r e 1. Luminescence from s i n g l e t oxygen i n a e r a t e d benzene solution. The s e n s i t i z e r was 2-acetonaphthone e x c i t e d a t 365 nm. The bandwidth a t FWHM i s 20 nm. Taken w i t h t h e a p p a r a t u s (Rodgers, M.A.J., t o be p u b l i s h e d ) shown i n f i g u r e 2.



82


Another p h y s i c a l t e c h n i q u e t h a t has r e c e n t l y been developed i s the use of t h e r m a l l e n s i n g . T h i s depends upon the d e a c t i v a t i o n of a p o p u l a t i o n o f e x c i t e d m o l e c u l e s by non.-radiative modes, _ i e , the e x c i t a t i o n energy i s r e l e a s e d t o the s u r r o u n d i n g medium as t h e r m a l energy. T h i s heat r e l e a s e , i f r a p i d enough, i e a f t e r l a s e r p u l s e e x c i t a t i o n , produces l o c a l changes i n t e m p e r a t u r e , d e n s i t y and r e f r a c t i v e index i n the medium. Thus the sample behaves momentari l y as a d i v e r g i n g l e n s and a c a r e f u l l y a l i g n e d o p t i c a l system can be s e t up t o probe the t r a n s i e n t l e n s and the r e s u l t i n g s i g n a l c o n t a i n s i n f o r m a t i o n on b o t h the k i n e t i c s of the n o n ^ r a d i a t i v e decay c h a n n e l s and on r e l a t i v e magnitudes of the c o n t r i b u t i o n s from the v a r i o u s decay modes. S i n c e s i n g l e t oxygen decays almost e x c l u s i v e l y n o n - r a d i a t i v e l y , i t i s p a r t i c u l a r l y w e l l ^ s u i t e d f o r thermal l e n s i n g s t u d i e s . Fuke, e t a l (36) f i r s t used t h i s t e c h n i q u e f o r k i n e t i c measurements and i t has r e c e n t l y been r e f i n e d and q u a n t i f i e d f o r y i e l d measurements by R o s s b r o i c h et a l (37). The method o f f e r s the c a p a b i l i t y o f measuring * and $T f o r p h o t o e x c i t e d molec u l e s by the r e l a t i v e l y s t r a i g h t f o r w a r d e x p e d i e n t o f measuring the slow heat c o n t r i b u t i o n i n a e r a t e d and d e - a e r a t e d s o l u t i o n s r e s p e c tively (37). A

APPARATUS FOR

INFRARED LUMINESCENCE MEASUREMENT

F u l l e r d e s c r i p t i o n s of the i n f r a r e d d e t e c t i o n methodology o c c u r elsewhere i n t h i s volume (3j3). B r i e f l y p r e s e n t e d here a r e two systems e x t a n t i n the a u t h o r s l a b o r a t o r y f o r c.w. and t i m e - r e s o l v e d quantum y i e l d measurements. 1

C.W.

EXCITATION

T h i s i s shown s c h e m a t i c a l l y i n F i g u r e 2 and i s a development o f systems used by Khan ( 3 9 ) , Kanofsky, (40) and H a l l and C h i g n e l l (Photochem. P h o t o b i o l . , i n p r e s s ) . S o l u t i o n s i n the 10mm x 10mm sample c u v e t t e are i r r a d i a t e d w i t h l i g h t from a 100W Hg a r c f i l r t e r e d through 10 cm of water and a heat a b s o r b i n g f i l t e r ( S c h o t t KG-3). T h i s c o m b i n a t i o n t r a n s m i t s mercury l i n e s a t 365 nm and above w i t h ca 90% e f f i c i e n c y but s t o p s r a d i a t i o n above 1000 nm w i t h h i g h e f f i c i e n c y . Luminescence i s c o l l e c t e d a t r i g h t a n g l e s by an Anaspec C a s s e g r a i n m i r r o r system ( f / 1 . 0 ) which conveys the l i g h t t o a monochromator ( O r i e l ) w i t h a 600 l i n e s per mm, 1.0 ym b l a z e g r a t ing. Monochromated r a d i a t i o n from the o u t p u t s l i t i s f o c u s s e d o n t o a 5mm germanium c r y s t a l PN d e t e c t o r c o u p l e d t o a transimpedance p r e a m p l i f i e r ( N o r t h Coast O p t i c a l Systems and S e n s o r s ) . B o t h det e c t o r s and p r e a m p l i f i e r a r e c o o l e d t o 77 K. T h i s system has a r e s p o n s i v i t y o f 5 x 109 v/W. THe d e t e c t o r i s covered by a 5 mm t h i c k d i s c of AR-coated h i g h p u r i t y s i l i c o n metal a c t i n g as an 1100 nm c u t - o f f f i l t e r . The e x c i t a t i o n beam i s chopped a t 100 Hz and the o u t p u t from the p r e a m p l i f i e r i s f e d t o a l o c k - i n a m p l i f i e r ( P r i n c e t o n A p p l i e d Research 124A) i n c o r p o r a t i n g a m u l t i r a n g e v o l t meter. A spectrum o f s i n g l e t oxygen measured w i t h t h i s i n s t r u m e n t i s shown i n F i g u r e 1. 2



RODGERS


F i g u r e 2. I n f r a r e d emission spectrophotometer schematic. L: 100W Hg a r c w i t h l e n s assembly; S: s h u t t e r ; Ch: v a r i a b l e f r e q u e n c y chopper; WF: 10 cm water f i l t e r ; F

Light-Activated Pesticides - ACS Publications - American Chemical

Recommend Documents